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Perovskite-type superlattices from lead halide perovskite nanocubes

Nature volume 593, pages 535–542 (2021)Cite this article

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Abstract

Atomically defined assemblies of dye molecules (such as H and J aggregates) have been of interest for more than 80 years because of the emergence of collective phenomena in their optical spectra1,2,3, their coherent long-range energy transport, their conceptual similarity to natural light-harvesting complexes4,5, and their potential use as light sources and in photovoltaics. Another way of creating versatile and controlled aggregates that exhibit collective phenomena involves the organization of colloidal semiconductor nanocrystals into long-range-ordered superlattices6. Caesium lead halide perovskite nanocrystals7,8,9 are promising building blocks for such superlattices, owing to the high oscillator strength of bright triplet excitons10, slow dephasing (coherence times of up to 80 picoseconds) and minimal inhomogeneous broadening of emission lines11,12. So far, only single-component superlattices with simple cubic packing have been devised from these nanocrystals13. Here we present perovskite-type (ABO3) binary and ternary nanocrystal superlattices, created via the shape-directed co-assembly of steric-stabilized, highly luminescent cubic CsPbBr3 nanocrystals (which occupy the B and/or O lattice sites), spherical Fe3O4 or NaGdF4 nanocrystals (A sites) and truncated-cuboid PbS nanocrystals (B sites). These ABO3 superlattices, as well as the binary NaCl and AlB2 superlattice structures that we demonstrate, exhibit a high degree of orientational ordering of the CsPbBr3 nanocubes. They also exhibit superfluorescence—a collective emission that results in a burst of photons with ultrafast radiative decay (22 picoseconds) that could be tailored for use in ultrabright (quantum) light sources. Our work paves the way for further exploration of complex, ordered and functionally useful perovskite mesostructures.

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Fig. 1: Characterization of a binary ABO3-type superlattice assembled from 8.6-nm CsPbBr3 and 19.5-nm Fe3O4 nanocrystals (γ = 0.420).
Fig. 2: Structural characterization of a binary ABO3-type superlattice.
Fig. 3: Characterization of a binary NaCl-type superlattice formed from 8.6-nm CsPbBr3 and 19.8-nm Fe3O4 nanocrystals (γ = 0.414).
Fig. 4: Characterization of a ternary ABO3-type superlattice assembled from 8.6-nm CsPbBr3, 10.7-nm PbS and 19.8-nm Fe3O4 nanocrystals.
Fig. 5: Superfluorescence from binary ABO3-type superlattices assembled from 8.6-nm CsPbBr3 and 16.5-nm NaGdF4 nanocrystals.

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Data availability

The data that support the findings of this study are available from the corresponding author on reasonable request.

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Acknowledgements

This work was primarily supported by the European Union through Horizon 2020 Research and Innovation Programme (ERC CoG Grant, grant agreement number 819740, project SCALE-HALO) and, in part, by the Swiss National Science Foundation (grant number 200021_192308, project Q-Light). We acknowledge the funding received from EU-H2020 under grant agreement number 654360 supporting the Transnational Access Activity within the framework NFFA-Europe to the TUG’s ELETTRA SAXS beamline of CERIC-ERIC. A.T. acknowledges the funding received from the National Science Foundation (USA) DMR-CMMT 1606336. We thank Y. Shynkarenko for assistance with high-resolution SEM imaging.

Author information

Authors and Affiliations

  1. Department of Chemistry and Applied Biosciences, Institute of Inorganic Chemistry, ETH Zürich, Zürich, Switzerland

    Ihor Cherniukh, Gabriele Rainò, Maryna I. Bodnarchuk & Maksym V. Kovalenko

  2. Laboratory of Thin Films and Photovoltaics, Empa – Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland

    Ihor Cherniukh, Gabriele Rainò, Maryna I. Bodnarchuk & Maksym V. Kovalenko

  3. IBM Research Europe — Zurich, Rüschlikon, Switzerland

    Thilo Stöferle & Rainer F. Mahrt

  4. Swiss Light Source, Paul Scherrer Institut, Villigen, Switzerland

    Max Burian

  5. Department of Physics and Astronomy, Iowa State University and Ames Lab, Ames, IA, USA

    Alex Travesset

  6. Institute of Inorganic Chemistry, Graz University of Technology, Graz, Austria

    Denys Naumenko & Heinz Amenitsch

  7. Electron Microscopy Center, Empa – Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland

    Rolf Erni

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  1. Ihor Cherniukh
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Contributions

M.V.K., M.I.B. and G.R. conceived and supervised the project. I.C. performed the synthesis and self-assembly experiments. I.C. and R.E. characterized the materials by electron microscopy. M.B., D.N. and H.A. characterized the materials by GISAXS. G.R., R.F.M. and T.S. carried out optical measurements. A.T. provided theoretical guidance and contributed to packing density analysis. I.C. and M.V.K. wrote the manuscript, with input from all authors.

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Correspondence to Maksym V. Kovalenko.

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Extended data figures and tables

Extended Data Fig. 1 Structural characterization of a binary ABO3-type superlattice (SL) of 8.6-nm CsPbBr3 and 14.5-nm Fe3O4 nanocrystals (γ = 0.541).

a, Low-magnification TEM image showing the large size of superlattice domains and homogeneous coverage over the carbon-coated TEM grid. b, TEM image of the area indicated by the box in a; upper inset is a higher-magnification TEM image; bottom inset is a small-angle ED pattern from a single superlattice domain in [001]SL projection. c, HAADF-STEM image of a [001]SL-oriented domain. d, EDX elemental maps of a [001]SL-oriented domain for Fe (grey, K line) and Pb (blue, L line). e, EDX line scans along the arrow in d. f, 2D GISAXS pattern showing long-range order. The superlattice reflections can be indexed using a tetragonal (P4/mmm) lattice: white markers correspond to the theoretical diffraction peak positions of a unit cell with a = b = 20.5 nm and c = 19.0 nm (red markers show the corresponding diffraction set for transmission channels, while white markers are for reflection channels; L defines the out-of-plane diffraction order).

Extended Data Fig. 2 Binary ABO3-type superlattice assembled from 8.6-nm CsPbBr3 and 16.5-nm NaGdF4 nanocrystals (γ = 0.486).

a, b, TEM images at different magnification of a superlattice domain deposited on a carbon-coated TEM grid; inset in b is a HAADF-STEM image. c, ED pattern from an area in b. ED reflections from CsPbBr3 confirm the ABO3 structure of the superlattice. d, e, SEM images at different magnification showing large-area coverage of the silicon substrate by binary superlattice domains; inset in e is a higher-magnification SEM image. f, Tilted SEM image revealing the thickness of the superlattice domain. The photoluminescence quantum yield of binary ABO3-type superlattices assembled from 8.6-nm CsPbBr3 and 16.5-nm NaGdF4 nanocrystals on sapphire substrates is about 50%, and rises above 70% after cooling with liquid nitrogen.

Extended Data Fig. 3 Binary AlB2-type superlattices.

a, AlB2 unit cell, along with crystallographic models of [001]- and [120]-oriented AlB2 lattices. Fe3O4 is shown as grey spheres and CsPbBr3 as blue cubes. b–d, 5.3-nm CsPbBr3 nanocrystals combined with 12.5-nm Fe3O4 nanocrystals (γ = 0.353). e, f, 8.6-nm CsPbBr3 nanocrystals combined with 19.8-nm Fe3O4 nanocrystals (γ = 0.414). b, TEM image of a superlattice domain in the [001]SL orientation. c–f, TEM images (c, e) of superlattice domains in the [120]SL orientation, along with the corresponding ED patterns (d, f). The inset in c shows a HAADF-STEM image. The presence of orthogonal reflections from the (110) and (111) lattice planes of CsPbBr3 indicates alignment of nanocubes in the superlattice such that the [111] and [110] crystallographic directions of CsPbBr3 orient along [001]SL and [100]SL, respectively.

Extended Data Fig. 4 Ternary ABO3-type superlattice domains assembled from 8.6-nm CsPbBr3, 10.7-nm PbS and 19.8-nm Fe3O4 nanocrystals.

a–d, [112]SL crystallographic orientation. e, f, [111]SL crystallographic orientation. g, h, [110]SL crystallographic orientation. a, e, g, HAADF-STEM images; insets show higher-magnification images. b–d, TEM image (b) of the [112]SL-oriented domain, along with the corresponding small-angle ED (c) and ED (d) patterns; the colour of diffraction arcs matches the nanocrystal orientations sketched as an inset in d (electron beam is normal to the plane of view). f, h, HAADF-STEM images and corresponding EDX-STEM maps for Fe (grey, K line), S (red, K line), Pb (blue, L line), Cs (green, L line) and Br (yellow, K line).

Extended Data Fig. 5 HAADF-STEM tilting series of a ternary ABO3-type superlattice of 8.6-nm CsPbBr3, 10.7-nm PbS and 19.8-nm Fe3O4 nanocrystals.

a, Tilting around the [010]SL axis. b, Tilting around the [110]SL axis. The HAADF-STEM images at different tilting angles match well with the corresponding projections of the CaTiO3 structure.

Extended Data Fig. 6 Transition from a binary ABO3 superlattice of 8.6-nm CsPbBr3 and 19.8-nm Fe3O4 nanocrystals to a ternary ABO3 superlattice of 8.6-nm CsPbBr3 and 25.1-nm Fe3O4 nanocrystals on incorporation of 10.7–11.7-nm truncated-cuboid PbS nanocrystals.

a, b, TEM image (a) and corresponding ED pattern (b) of a single binary [001]SL-oriented domain assembled from 8.6-nm CsPbBr3 and 19.8-nm Fe3O4 nanocrystals. Inset in a, model of the binary ABO3 lattice. c, d, TEM image (c) and corresponding ED pattern (d) of a single ternary [001]SL-oriented domain assembled from 8.6-nm CsPbBr3, 10.7-nm PbS and 19.8-nm Fe3O4 nanocrystals. Inset in c, model of the ternary ABO3 structure, showing the formation of a solid solution by substitution of CsPbBr3 nanocrystals on the B site of the lattice by PbS nanocrystals. The number ratio of PbS to CsPbBr3 nanocrystals in the mixture is too small to form an exclusively ternary superlattice. As a result, CsPbBr3 and PbS nanocrystals are both present on B sites, as is evident from ED patterns. In the ED pattern of the partially ternary lattice, the intensity of the (110) reflection ‘1d’, which originates from only the centre CsPbBr3, is weakened compared to reflection ‘1b’ in the ED pattern of the binary superlattice, because the number of perovskite nanocrystals on B sites is reduced. By contrast, the intensity of the (220) reflection ‘2d’, which originates from CsPbBr3 and PbS nanocrystals located on B sites, is enhanced compared to reflection ‘2b’ in the ED pattern of the binary superlattice, because the scattering from PbS nanocrystals, which contributes to this peak, is stronger than from the CsPbBr3 lattice. As the degree of substitution increases, (111), (200) and (220) ED reflections for CsPbBr3 and PbS nanocrystals add up (because of similar lattice parameters) and give rise to higher intensity, whereas the (100) and (110) reflections, to which PbS nanocrystals do not contribute owing to their Fm\(\bar{3}\)m symmetry, eventually vanish (Fig. 4d, Supplementary Fig. 5q, t). e, TEM and HAADF-STEM (bottom inset) images of a single ternary [001]SL-oriented ABO3 domain assembled from 8.6-nm CsPbBr3, 11.7-nm PbS and 25.1-nm Fe3O4 nanocrystals. f, Respective ED and small-angle ED (inset) patterns. Upper inset in e, model of the ternary ABO3 lattice. 25.1-nm Fe3O4 nanocrystals are too large to form a binary ABO3-type superlattice. However, the addition of 11.7-nm truncated-cuboid PbS nanocrystals makes the ternary ABO3-type superlattice stable.

Extended Data Fig. 7 Ternary ABO3-type superlattice domains assembled from 8.6-nm CsPbBr3, 11.7-nm PbS and 21.5-nm Fe3O4 nanocrystals.

a, b, TEM image (a) of a single superlattice domain in the [001]SL orientation and the corresponding small-angle ED (a, inset) and ED (b) patterns. c, Low-magnification and high-magnification (inset) HAADF-STEM images of [001]SL-oriented domains. d, e, HAADF-STEM images of [101]SL-oriented (d) and [112]SL-oriented (e) domains.

Extended Data Fig. 8 TEM images of columnar binary superlattices assembled from 5.3-nm CsPbBr3 cubes and LaF3 nanodisks.

a, AB(I)-type superlattice of 16.6-nm LaF3 nanocrystals. b, AB2(I)-type superlattice of 26.5-nm LaF3 nanocrystals. c, ABx-type superlattice of 12.5-nm LaF3 nanocrystals. d, AB(II)-type superlattice of 9.2-nm LaF3 nanocrystals. e, AB2(II)-type superlattice of 12.5-nm LaF3 nanocrystals. f, AB6-type superlattice of 21.0-nm LaF3 nanocrystals. Structural models of the superlattices are presented as insets. Six different columnar structures are observed, as a result of adjusting the cube-to-disk size and number ratios. None of these structures had previously been reported for disk–sphere systems and nor observed by us, highlighting the crucial role of the cubic shape for the formation of these structures (owing to a much higher resulting packing density compared to disk–sphere systems). However, the yield and the lateral extent of the superlattice grains are considerably smaller than those of ABO3- and NaCl-type superlattices and require further optimization.

Extended Data Fig. 9 Luminescence spectroscopy of ABO3-type binary superlattices made from 8.6-nm CsPbBr3 and 16.5-nm NaGdF4 nanocrystals on a carbon-coated Cu grid.

a, Photoluminescence (PL) spectrum, which, similarly to Fig. 5, is composed of two bands (coupled and uncoupled nanocrystals). b, Photoluminescence intensity for the uncoupled (blue circles) and coupled (red circles) nanocrystal bands, on a logarithmic scale. Fits to the data (red solid lines) reveal sublinear behaviour, with fitted power-law exponents m ≈ 0.4–0.5. These exponents differ from those when using Si3N4 as a substrate, indicative of non-radiative processes at higher fluences and much enhanced superlattice–substrate interaction in the case of a conductive carbon film. c, Streak camera images obtained with an excitation fluence of 175 μJ cm−2. In contrast to the results reported in the main text for ABO3-type superlattices on Si3N4-membranes, no evidence of drastic shortening or time oscillations was found. Furthermore, a pronounced dynamic redshift characterizes the initial decay, which could be related to thermal effects (rapid cooling after heating through the excitation pulse). This is in stark contrast with typical superfluorescence spectral dynamics13 (Fig. 5), which exhibits a dynamic blueshift versus time13. d, Spectrally integrated time-resolved emission intensity traces for two excitation fluences (8 μJ cm−2, black; 175 μJ cm−2, red). Although a slight shortening of the decay is clearly observed, this is probably due to a non-radiative process, presumably energy transfer to the substrate, given the sublinear fluence dependence observed in b and the reduction of the fluorescence lifetime of uncoupled nanocrystals from 350 ps to about 100 ps even at low fluences. Carbon-coated grids might introduce absorbing states, which strongly influence the exciton dynamics and the onset of superfluorescence emission. This pronounced substrate effect is unsurprising given that superlattices are morphologically two-dimensional, being at most 10 unit cells in thickness.

Extended Data Fig. 10 Emission properties of different binary superlattices of 8.6-nm perovskite nanocrystals.

a, b, d, e, g, h, Fluence-dependent photoluminescence (a, d, g) and time-resolved photoluminescence traces (b, e, h) for NaCl-type superlattices with 18.6-nm NaGdF4 nanocrystals (a, b), ABO3-type superlattices with 15.2 nm NaGdF4 nanocrystals (d, e) and ABO3-type superlattices with 19.5-nm NaGdF4 nanocrystals (g, h). c, f, i, Corresponding typical streak camera images obtained at high fluences. See Supplementary Note 4 for a discussion of the results.

Supplementary information

Supplementary Information

This file contains Supplementary Notes 1-4, Supplementary Tables 1, 2, Supplementary Figures 1-14 and Supplementary References. It includes additional data and discussion on calculation of packing densities of SL structures, relationship between lattice planes and facets in CsPbBr3 nanocubes, GISAXS characterization of SLs, superfluorescence in various binary SLs, TEM characterization of SLs.

Supplementary Video 1

Tomographic reconstruction of binary ABO3-type SL. ABO3-type binary SL domain comprising 8.6 nm CsPbBr3 nanocubes and 19.5 nm NaGdF4 spherical NCs reconstructed from electron tomography. The orientation of B- and O-site cubes is resolvable.

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Cherniukh, I., Rainò, G., Stöferle, T. et al. Perovskite-type superlattices from lead halide perovskite nanocubes. Nature 593, 535–542 (2021). https://doi.org/10.1038/s41586-021-03492-5

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